TW202033658A - Resin composition and uses of the same - Google Patents

Abstract

A resin composition is provided. The resin composition comprises the following constituents: (A) a polyphenylene ether resin with unsaturated end groups; (B) a constituent having a maleimide structure; (C) a first initiator, which has a first one-minute half-life temperature; and (D) a second initiator, which has a second one-minute half-life temperature, wherein the first one-minute half-life temperature is 20 DEG C to 50 DEG C higher than the second one-minute half-life temperature, and the first one-minute half-life temperature is 170 DEG C to 220 DEG C.

Description

Resin composition and its application

The present invention provides a resin composition, and particularly relates to a polyphenylene ether resin composition containing two kinds of initiators with specific half-life temperatures. The resin composition of the present invention can be combined with a reinforcing material to form a composite material or a prepreg, or can be further used as an adhesive for metal foil to prepare metal-clad laminates and printed circuit boards (PCBs). ).

The metal foil laminate is one of the commonly used materials for manufacturing printed circuit boards, and can be prepared, for example, by the following method. First, the reinforcing material (for example, glass fabric) is impregnated in a thermosetting resin composition (for example, a polyphenylene ether resin composition) or the thermosetting resin composition is coated on the reinforcing material, and baked through the resin The composition is impregnated or coated with a reinforcing material to a semi-cured state (ie, B-stage) to form a prepreg. Subsequently, a predetermined number of prepregs are laminated to provide a dielectric layer. Laminate a metal foil (such as copper foil) on at least one outer side of the dielectric layer to provide a laminate, and then perform a hot pressing operation (ie C-stage) on the laminate to obtain a Metal foil laminated board.

Recently, the demand for data transmission in the field of electronic communication technology has continued to increase, causing the application of electronic products to enter the field of high-frequency and high-speed transmission. Under the trend of high frequency and high speed signal transmission, miniaturization of electronic components, and high density of circuit board circuits, the requirements for the dielectric properties and storage stability of related electronic materials have also been increasing. In order to obtain a high-density printed circuit board, the printed circuit board is usually formed as a multilayer structure to lay as many circuits as possible. The multilayer board (ie, a printed circuit board with a multilayer structure) can be prepared in the following manner. First, a suitable conductive material (such as metal foil) and a dielectric material (such as a prepreg) are pressed to form a core layer, and the core layer is patterned. Subsequently, a build-up structure is formed using appropriate conductive materials (such as metal foil) and dielectric materials (such as prepregs). The build-up structure is sequentially stacked and pressed onto the core layer, and then the build-up structure is also patterned to form a multilayer board. The above method is also called the build-up method. However, the build-up method requires a long process time. If the storage stability of the dielectric material (such as the prepreg) is not good, the prepreg may be aged due to the cross-linking reaction to a certain extent before pressing (ie, dynamic viscosity). Too high), resulting in the prepreg cannot be smoothly bonded to the metal foil. In addition, if the prepreg needs a longer pressing time to reach a fully cured state during the pressing process, it will increase the process time, resulting in increased process costs and decreased yield.

The invention provides a thermosetting resin composition and a prepreg, a metal foil laminated board and a printed circuit board prepared by using the same. The technical means of the present invention to solve the problem is to combine two kinds of initiators with different half-life temperatures and the half-life temperature difference within a specific range in the polyphenylene ether resin composition. The prepreg prepared by the resin composition of the present invention will not age after being placed for a long time and has a suitable dynamic viscosity, excellent storage stability, and the prepared prepreg has the required pressure when preparing metal foil laminates. The combination time is short, which can reduce the process cost and increase the yield. In addition, the prepared electronic material can have satisfactory dielectric properties and heat resistance properties. Therefore, the present invention relates to the following inventive objects.

One object of the present invention is to provide a resin composition comprising the following components: (A) Polyphenylene ether resin with unsaturated groups at the end; (B) Ingredients with maleimide structure; (C) a first initiator, the first initiator having a first 1-minute half-life temperature; and (D) The second initiator, which has a second 1-minute half-life temperature, The first 1-minute half-life temperature is higher than the second 1-minute half-life temperature by 20°C to 50°C, and the first 1-minute half-life temperature is 170°C to 220°C.

In some embodiments of the present invention, the first 1-minute half-life temperature is 21°C to 35°C higher than the second 1-minute half-life temperature, and the first 1-minute half-life temperature is 170°C to 190°C.

In some embodiments of the present invention, the weight ratio of the first initiator (C) to the second initiator (D) is 6:1 to 1:6, preferably 6:1 to 3:4 , More preferably 6:1 to 4:3.

式（I）， 於式（I）中， R₃ 、R₄ 、R₅ 、及R₆ 係各自獨立為H、或經或未經取代之C1至C5烷基，且R₃ 、R₄ 、R₅ 、及R₆ 較佳為-CH₃ ； m與n各自獨立為0至100的整數，條件為m與n不同時為0； Z為不存在、-O-、

、

、

、

、

、或芳基（aryl），其中R₇ 與R₈ 係各自獨立為H或C1至C12烷基，且Z較佳為

； X與Y係各自獨立為不存在、羰基（carbonyl group）、或具有烯基之基團，且X與Y較佳為不存在；以及 A₁ 與A₂ 係各自獨立為

、、

、

、

或

，且A₁ 與A₂ 較佳為

或

。In some embodiments of the present invention, the polyphenylene ether resin (A) with an unsaturated group at the end is represented by the following formula (I):

Formula (I), in formula (I), R ₃ , R ₄ , R ₅ , and R ₆ are each independently H, or a C1 to C5 alkyl group that is or unsubstituted, and R ₃ , R ₄ , R ₅ and R _{6 are} preferably -CH ₃ ; m and n are each independently an integer from 0 to 100, provided that m and n are not 0 at the same time; Z is absent, -O-,

,

,

,

,

, Or aryl (aryl), wherein R ₇ and R ₈ are each independently H or C1 to C12 alkyl, and Z is preferably

; X and Y are each independently absent, a carbonyl group, or a group with alkenyl, and X and Y are preferably absent; and A ₁ and A ₂ are each independently

,,

,

,

or

, And A ₁ and A _{2 are} preferably

or

.

In some embodiments of the present invention, the component (B) having a maleimide structure is selected from the following groups: 1,2-bismaleimide ethane, 1,6-bismaleimide Leximinohexane, 1,3-bismaleimidobenzene, 1,4-bismaleimidobenzene, 2,4-bismaleimidotoluene, 4,4 '-Bismaleimidodiphenylmethane, 4,4'-bismaleimidodiphenyl ether, 3,3'-bismaleimidodiphenylmethane, 4, 4'-bismaleimidodiphenyl sulfide, 4,4'-bismaleimidodicyclohexylmethane, 3,5-bis(4-maleimidphenyl)pyridine , 2,6-bismaleiminopyridine, 1,3-bis(maleiminomethyl)cyclohexane, 1,3-bis(maleiminomethyl)benzene, 1,1-bis(4-maleimidphenyl)cyclohexane, 1,3-bis(dichloromaleimidyl)benzene, 4,4'-dicitraconyl Diphenylmethane (4,4'-biscitraconimidodiphenylmethane), 2,2-bis(4-maleiminophenyl) propane, 1-phenyl-1,1-bis(4-maleimide) Phenyl)ethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-dibenzyl bismaleimide, α,α-bis(4-male Leximinophenyl) toluene, 3,5-bismaleimino-1,2,4-triazole, N,N'-ethylenebismaleimide, N,N' -Hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N' -4,4'-Diphenylmethane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N'-4,4'-diphenyl Base bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-α,α'-4,4'-dimethylene ring Hexane bismaleimide, N,N'-m-xylene bismaleimide, N,N'-4,4'-diphenylcyclohexane bismaleimide, N,N '-Methylene bis(3-chloro-p-phenylene) bismaleimide, and combinations of the foregoing.

In some embodiments of the present invention, the first initiator (C) is selected from the following group: 4,4-di(tertiarybutylperoxy) n-butyl valerate (n-butyl 4,4) -bis(tert-butylperoxy)valerate) (1 minute half-life temperature: 172.5°C), tert-butylcumyl peroxide (1 minute half-life temperature: 173.3°C), two peroxide Cumene (dicumyl peroxide) (1 minute half-life temperature: 175.2°C), 1,3-bis-(2-tertiary butylperoxyisopropyl)benzene (1,3-di-(2-tert- butyl-peroxyisopropyl)benzene) (1 minute half-life temperature: 175.4°C), 2,5-dimethyl-2,5-di-(tertiary butylperoxy) hexane (2,5-dimethyl-2, 5-di-(tert-butylperoxy)hexane) (1 minute half-life temperature: 179.8°C), di-tert-butylperoxide (1 minute half-life temperature: 185.9°C), 2 ,5-Dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne) (1 minute Half-life temperature: 194.3°C), diisopropylbenzene hydroperoxide (1 minute half-life temperature: 207°C), p-menthane hydroperoxide (1 minute half-life temperature: 199.5 °C), and the aforementioned combination.

In some embodiments of the present invention, the second initiator (D) is selected from the following group: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate ( 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate) (1 minute half-life temperature: 124.3°C), tert-amylperoxy-2-ethylhexanoate (tert-amylperoxy-2-ethylhexanoate) (1 One minute half-life temperature: 128°C), dibenzoyl peroxide (1 minute half-life temperature: 130°C), tert-hexylperoxy-2-ethylhexanoate (tert-hexylperoxy-2- ethylhexanoate (1 minute half-life temperature: 132.6°C), tert-butylperoxy-2-ethylhexanoate (1 minute half-life temperature: 134°C), tri-peroxide Tert-butylperoxyisobutyrate (1 minute half-life temperature: 136°C), 1,1-bis(tertiary butylperoxy)-3,3,5-trimethylcyclohexane ( 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane) (1 minute half-life temperature: 148°C), 1,1-di(tert-butylperoxy) cyclohexane (1,1- di(tert-hexylperoxy)cyclohexane) (1 minute half-life temperature: 149.2°C), tert-amylperoxy-2-ethyl hexylcarbonate (tert-amylperoxy-2-ethyl hexylcarbonate) (1 minute half-life temperature: 151 °C), 1,1-di(tert-butylperoxy)cyclohexane (1,1-di(tert-butylperoxy)cyclohexane) (1 minute half-life temperature: 153.8°C), tert-butylperoxy Isopropyl carbonate (tert-butylperoxyisopropylcarbonate) (1 minute half-life temperature: 158.8°C), 2,2-di(tert-butylperoxy)butane (2,2-di(tert-butylperoxy)butane) ( 1 minute half-life temperature: 159.9°C), tert-butylperoxyacetate (1 minute half-life temperature: 159.9°C), tert-butylperoxy-2-ethylhexyl carbonate (tert-butylperoxyacetate) -butylperoxy-2-ethylhexylcarbonate) (1 minute half-life temperature: 16 1.4°C), tert-butylperoxy-3,3,5-trimethylhexanoate (1 minute half-life temperature: 166°C), tertiary Tert-butylperoxybenzoate (1 minute half-life temperature: 166.8°C), di-tert-amylperoxide (1 minute half-life temperature: 169°C) , Tertiary butyl cumene peroxide, dicumyl peroxide, 1,3-bis-(2-tertiary butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5 -Di(tertiary butyl peroxide) hexane, di-tertiary butyl peroxide, 2,5-dimethyl-2,5-bis(tertiary butyl peroxide)-3-hexyne, And the aforementioned combination.

In some embodiments of the present invention, the resin composition further includes a crosslinking agent selected from the following groups: polyfunctional allylic compound, polyfunctional acrylate, polyfunctional acrylate, and polyfunctional allylic compound. Functional acrylamide (polyfunctional acrylamide), polyfunctional styrenic compound (polyfunctional styrenic compound), and a combination of the foregoing.

In some embodiments of the present invention, the resin composition further includes a flame retardant selected from the group consisting of phosphorus-containing flame retardants, bromine-containing flame retardants, nitrogen-containing compounds, and combinations of the foregoing.

In some embodiments of the present invention, the resin composition further includes a filler selected from the following group: silica, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, aluminum oxide, and hydroxide Aluminum, boron nitride, silicon nitride, aluminum silicon carbide, silicon carbide, sodium carbonate, magnesium carbonate, titanium dioxide, zinc oxide, zirconia, quartz, diamond powder, diamond-like powder, graphite, calcined kaolin, bailing clay, mica, Hydrotalcite, polytetrafluoroethylene (PTFE) powder, glass beads, ceramic whiskers, carbon nanotubes, nano-grade inorganic powder, and combinations of the foregoing.

Another object of the present invention is to provide a prepreg, which is prepared by impregnating or coating a substrate with the above-mentioned resin composition, and drying the impregnated or coated substrate.

Another object of the present invention is to provide a metal foil laminated board, which is produced by laminating the above-mentioned prepreg and metal foil.

Another object of the present invention is to provide a printed circuit board, which is produced by the metal foil laminate as described above.

In order to make the above objectives, technical features and advantages of the present invention more obvious and understandable, the following is a detailed description of some specific implementation aspects.

The following will specifically describe some specific implementation aspects of the present invention; however, without departing from the spirit of the present invention, the present invention can still be practiced in many different forms, and the protection scope of the present invention should not be limited to the specific embodiments. Implementation status.

Unless otherwise stated in the text, the terms "a", "the" and similar terms used in this specification (especially in the scope of the appended patent application) shall be understood to include singular and plural forms.

Unless otherwise stated, in this specification (especially in the scope of the patent application described below), the terms "first", "second" and similar terms used are only used to distinguish the described elements or components, and are not themselves It has no special meaning, and it is not intended to refer to a sequence.

Unless otherwise stated in the text, when the components contained in the solution, mixture or composition are described in this specification, the solid content is calculated, that is, the weight of the solvent is not included.

In this article, the term "resin solid content" refers to the excluding all solid components other than fillers in the resin composition, that is, including polyphenylene ether resin (A) with an unsaturated group at the end and maleimide Structural components (B), first starter (C), second starter (D) and other necessary components, as well as optional components (such as crosslinking agent and flame retardant) as needed.

The effect of the present invention in comparison with the prior art is that the resin composition of the present invention uses a combination of polyphenylene ether resin, a component with a maleimide structure, and two initiators with a specific half-life temperature difference, thereby making the prepared The prepreg has good storage stability and a shorter required pressing time, thereby reducing costs and increasing yield, and the prepared electronic materials also have satisfactory dielectric properties and heat resistance. The following provides a detailed description of the components and preparation methods of the resin composition of the present invention.

1. Resin composition

The resin composition of the present invention comprises a polyphenylene ether resin (A) having an unsaturated group at the end, a component (B) having a maleimide structure, a first initiator (C) and a second initiator (D) And other necessary ingredients, and other optional ingredients as needed.

1.1. Polyphenylene ether resin with unsaturated groups at the end ( A )

且在末端具有不飽和基團的樹脂，其中R各自獨立為H或C1至C5的烷基，且v為1至100之整數。所述不飽和基團係指能夠與其他具有不飽和基團之成分發生加成聚合反應之基團，所述加成聚合反應可於存在有聚合起始劑之情況下藉由光或熱而引發。不飽和基團的實例包括但不限於乙烯基（vinyl）、乙烯苄基（vinyl benzyl）、烯丙基（allyl）、丙烯酸酯基（acrylic）、及甲基丙烯酸酯基（methacrylic）。末端具有不飽和基團的聚苯醚樹脂的實例包括但不限於含乙烯基之聚苯醚樹脂、含烯丙基之聚苯醚樹脂、含乙烯苄基之聚苯醚樹脂、含丙烯酸酯基之聚苯醚樹脂、及含甲基丙烯酸酯基之聚苯醚樹脂。各該聚苯醚樹脂可單獨使用或任意組合使用。In this article, polyphenylene ether resin with unsaturated groups at the end means that it has at least repeating units in the main chain of the molecule

A resin having an unsaturated group at the end, wherein R is each independently H or a C1 to C5 alkyl group, and v is an integer from 1 to 100. The unsaturated group refers to a group capable of undergoing an addition polymerization reaction with other components having an unsaturated group. The addition polymerization reaction can be caused by light or heat in the presence of a polymerization initiator. Trigger. Examples of unsaturated groups include, but are not limited to, vinyl, vinyl benzyl, allyl, acrylic, and methacrylic. Examples of polyphenylene ether resins with unsaturated groups at the end include, but are not limited to, vinyl-containing polyphenylene ether resins, allyl-containing polyphenylene ether resins, vinylbenzyl-containing polyphenylene ether resins, and acrylate-containing The polyphenylene ether resin and the polyphenylene ether resin containing methacrylate groups. Each of the polyphenylene ether resins can be used alone or in any combination.

The preparation method of the polyphenylene ether resin with unsaturated groups at the end is not the technical focus of the present invention, and it is the method that can be carried out by those with ordinary knowledge in the technical field to which the present invention pertains based on the disclosure and general knowledge of this specification. This is not repeated here. Documents related to the preparation of polyphenylene ether resins with unsaturated groups at the end include US 6,995,195 B2 (polyphenylene ether resin containing vinyl benzyl groups), US 5,218,030 A (polyphenylene ether resin containing allyl groups), US 5,352,745 A (polyphenylene ether resin containing methacrylate group), US 6,352,782 B2, and US 2016/0280913 A1, these documents are hereby incorporated by reference in their entirety.

式（I）。In some embodiments of the present invention, the polyphenylene ether resin (A) with an unsaturated group at the end is represented by the following formula (I):

Formula (I).

、

、

、

、

、或芳基，其中R₇ 與R₈ 係各自獨立為H或C1至C12烷基；X與Y係各自獨立為不存在、羰基、或具有烯基之基團；以及A₁ 與A₂ 係各自獨立為

、、

、

、

或

。於本發明之較佳實施態樣中，式（I）之R₃ 、R₄ 、R₅ 、及R₆ 為-CH₃ ，Z為

，X與Y為不存在，且A₁ 與A₂ 各自獨立為

或

。In formula (I), R ₃ , R ₄ , R ₅ , and R ₆ are each independently H, or a C1 to C5 alkyl group which may be substituted or unsubstituted; m and n are each independently an integer from 0 to 100, The condition is that m and n are not 0 at the same time; Z is not present, -O-,

,

,

,

,

, Or aryl group, wherein R ₇ and R ₈ are each independently H or C1 to C12 alkyl; X and Y are each independently a non-existent, carbonyl, or alkenyl group; and A ₁ and A ₂ are Each independently

,,

,

,

or

. In a preferred embodiment of the present invention, R ₃ , R ₄ , R ₅ , and R ₆ of formula (I) are -CH ₃ , and Z is

, X and Y are not present, and A ₁ and A ₂ are each independently

or

.

In the resin composition of the present invention, the weight average molecular weight (Mw) of the polyphenylene ether resin (A) having an unsaturated group at the end may be 1,000 to 50,000, preferably 1,000 to 10,000, and more preferably 1000 to 5000. If the Mw of the polyphenylene ether resin is higher than the above range (for example, higher than 50000), the fluidity, solubility, etc. of the resin composition may deteriorate, causing difficulties in subsequent processing. Conversely, if the Mw of the polyphenylene ether resin is lower than the above range (for example, lower than 1000), the dielectric properties and thermal stability of the resin composition may deteriorate.

Examples of commercially available polyphenylene ether resins (A) with unsaturated groups at the ends include products of OPE-2st and OPE-2EA available from MITSUBISHI GAS CHEMICAL, available from SABIC's products with model number SA-9000 can be purchased from Jinyi Chemical's products with model number PP807, and polyphenylene ether products can be purchased from ASAHI KASEI.

In the resin composition of the present invention, based on 100 parts by weight of the resin solid content, the content of the polyphenylene ether resin (A) having an unsaturated group at the end may be 20 parts by weight to 70 parts by weight, more specifically 25 parts by weight. Parts by weight to 65 parts by weight, such as 27 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 45 parts by weight, 47 parts by weight, 50 parts by weight, 53 parts by weight Parts, 55 parts by weight, 58 parts by weight, 60 parts by weight, or 63 parts by weight.

1.2. Ingredients with maleimide structure ( B )

式（II）。Herein, the maleimine structure refers to an unsaturated amide structure having a reactive double bond. The component having a maleimide structure can react with other components having an unsaturated group because it has a reactive double bond. In some embodiments of the present invention, the component (B) having a maleimide structure includes one or more compounds represented by the following formula (II):

Formula (II).

）、間伸苯基（

）、雙酚A二苯醚基（

）、3,3'-二甲基-5,5'-二乙基-4,4'-二苯甲烷基（

）、4-甲基-1,3-伸苯基（

）、及（2,2,4-三甲基）-1,6-伸己基（

）。In formula (II), M ₁ is an organic group, and R ₁ and R ₂ are each independently H, halogen, or C1 to C5 alkyl. Specifically, M ₁ is a divalent group of C2 to C40, and the divalent group includes but is not limited to a divalent aliphatic group, a divalent alicyclic group, a divalent aromatic group or a divalent aromatic group. Heterocyclic group. In a preferred embodiment of the present invention, R ₁ and R ₂ are H, and M ₁ is selected from the following group: methylene (-CH ₂ -), 4,4'-diphenylmethyl (

), meta-phenylene (

), bisphenol A diphenyl ether group (

), 3,3'-dimethyl-5,5'-diethyl-4,4'-dibenzyl (

), 4-methyl-1,3-phenylene (

), and (2,2,4-trimethyl)-1,6-hexylene (

).

））。Specific examples of the compound represented by the formula (II) include, but are not limited to, 1,2-bismaleiminoethane, 1,6-bismaleiminohexane, 1,3-bismaleimide Aminobenzene, 1,4-bismaleimidinylbenzene, 2,4-bismaleimidinyl toluene, 4,4'-bismaleimidinodiphenylmethane, 4 , 4'-bismaleimid diphenyl ether, 3,3'-bismaleimid diphenyl ether, 4,4'-bismaleimid diphenyl ether, 4,4'-bismaleimidodicyclohexylmethane, 3,5-bis(4-maleimidphenyl)pyridine, 2,6-bismaleimidpyridine, 1 ,3-Bis(maleiminomethyl)cyclohexane, 1,3-bis(maleimidinyl)benzene, 1,1-bis(4-maleimidinylbenzene) Base) cyclohexane, 1,3-bis(dichloromaleimidyl)benzene, 4,4'-dicitraconylimidodiphenylmethane, 2,2-bis(4-maleimidyl) Aminophenyl) propane, 1-phenyl-1,1-bis(4-maleimidphenyl)ethane, 3,3'-dimethyl-5,5'-diethyl -4,4'-Dibenzyl bismaleimide, α,α-bis(4-maleiminophenyl) toluene, 3,5-bismaleimino-1 ,2,4-triazole, N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bis Maleimide, N,N'-p-phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4 ,4'-Diphenyl ether bismaleimide, N,N'-4,4'-diphenyl bismaleimide, N,N'-4,4'-dicyclohexylmethane Bismaleimide, N,N'-α,α'-4,4'-dimethylcyclohexane bismaleimide, N,N'-m-xylene bismaleimide , N,N'-4,4'-diphenylcyclohexane bismaleimide, and N,N'-methylene bis(3-chloro-p-phenylene) bismaleimide amine. Each of these compounds can be used alone or in any combination. In the following examples, 3,3'-dimethyl-5,5'-diethyl-4,4'-dibenzyl bismaleimide (ie, formula (II) R ₁ and R ₂ are H, and M ₁ is 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethyl (

)).

In the resin composition of the present invention, based on 100 parts by weight of the resin solid content, the content of the maleimide structure component (B) may be 20 parts by weight to 70 parts by weight, more specifically 25 parts by weight To 65 parts by weight, such as 27 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 55 parts by weight, 58 parts by weight, 60 parts by weight, or 62 parts by weight.

1.3. The first initiator ( C ) And the second initiator ( D )

Although the polymerization reaction may be initiated thermally without the presence of a polymerization initiator, it usually requires extremely high temperatures to perform the polymerization reaction without a polymerization initiator. However, due to the limitation of temperature, it is difficult to carry out the polymerization reaction without polymerization initiator under the industrial process conditions of general electronic materials. Therefore, under the general industrial process conditions of electronic materials, the polymerization reaction is usually carried out in the presence of a polymerization initiator. Herein, the initiator refers to a substance that can initiate a polymerization reaction, and can be roughly classified into a photoinitiator and a thermal initiator. Examples of photoinitiators include, but are not limited to, onium salts, diazonium salts, benzoin ethers, aromatic ketones, and metal organics. Examples of thermal initiators include, but are not limited to, organic peroxy compounds and azos. Organic peroxides are thermally unstable substances, which tend to accelerate their decomposition as the temperature rises. Therefore, the reaction characteristics of organic peroxides can usually be expressed by the "half-life temperature". Specifically, the half-life temperature can be divided into a 1-minute half-life temperature, a 1-hour half-life temperature, and a 10-hour half-life temperature according to the length of the decomposition time. The 1-minute half-life temperature indicates that a certain amount of organic peroxide can be obtained at this temperature. Decompose to half of the initial amount within 1 minute.

The 1-minute half-life temperature of the organic peroxide can be measured in a manner known to those skilled in the art to which the present invention belongs. Specifically, the organic peroxide can be dissolved in an inert solvent to form an organic peroxide solution with a concentration of 0.1 mol/liter (mol/L), and the differential scanning calorimeter-thermal activity meter ( differential scanning calorimetry-thermal activity monitoring, DSC-TAM) to determine the temperature at which the decomposition amount of organic peroxides can reach 50% of the initial amount within 1 minute. The inert solvent used may be benzene or chlorobenzene.

The resin composition of the present invention uses two different starters to improve the storage stability and required pressing time of the prepared prepreg. The starter with a higher one-minute half-life temperature is called the first starter (C), the initiator with a lower one-minute half-life temperature is called the second initiator (D). The first initiator (C) has a first 1-minute half-life temperature between 170°C and 220°C, preferably a first 1-minute half-life temperature between 170°C and 210°C, and More preferably, it has a first 1-minute half-life temperature between 170°C and 190°C. The second initiator (D) has a second 1-minute half-life temperature that is 20°C to 50°C lower than the first 1-minute half-life temperature. In other words, the first 1-minute half-life temperature is 20°C to 50°C higher than the second 1-minute half-life temperature. In a preferred embodiment of the present invention, the first 1-minute half-life temperature is 21°C to 35°C higher than the second 1-minute half-life temperature, such as 22°C, 23°C, 24°C, 25° C, 26°C, 27°C, 28°C, 29°C, 30°C, 31°C, 32°C, 33°C, or 34°C. When the first 1-minute half-life temperature is within the specified range and the difference between the first 1-minute half-life temperature and the second 1-minute half-life temperature is also within the specified range, the prepreg made from the resin composition can have excellent storage stability And a shorter required pressing time, that is, a proper balance can be achieved between storage stability and required pressing time. Conversely, when the first 1-minute half-life temperature is not within the specified range or the difference between the first 1-minute half-life temperature and the second 1-minute half-life temperature is not within the specified range, the prepared prepreg may not have excellent storage stability at the same time And the shorter required pressing time, that is, the proper balance between storage stability and required pressing time will not be reached.

Examples of the first initiator (C) include but are not limited to n-butyl 4,4-di(tertiarybutylperoxy)valerate (1 minute half-life temperature: 172.5°C), isopropyl tertiary butyl peroxide Benzene (1 minute half-life temperature: 173.3°C), dicumyl peroxide (1 minute half-life temperature: 175.2°C), 1,3-bis-(2-tertiary butylperoxyisopropyl)benzene ( 1 minute half-life temperature: 175.4°C), 2,5-dimethyl-2,5-di-(tertiary butylperoxy) hexane (1 minute half-life temperature: 179.8°C), di-tertiary butyl Peroxide (1 minute half-life temperature: 185.9°C), 2,5-Dimethyl-2,5-bis(tertiary butylperoxy)-3-hexyne (1 minute half-life temperature: 194.3°C) ), dicumyl benzene hydroperoxide (1 minute half-life temperature: 207°C), and p-menthane hydroperoxide (1 minute half-life temperature: 199.5°C). Each of the initiators can be used alone or in any combination.

Specific examples of the second initiator (D) include but are not limited to 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1 minute half-life temperature: 124.3°C), Oxidized tertiary pentyl-2-ethylhexanoate (1 minute half-life temperature: 128°C), dibenzyl peroxide (1 minute half-life temperature: 130°C), tertiary hexyl peroxide-2-ethyl Hexanoate (1 minute half-life temperature: 132.6°C), tertiary butylperoxy-2-ethylhexanoate (1 minute half-life temperature: 134°C), tertiary butyl peroxide (1 minute half-life temperature: 136°C), 1,1-bis(tertiary butyl peroxide)-3,3,5-trimethylcyclohexane (1 minute half-life temperature: 148°C), 1, 1-Di(tertiary hexyl peroxide) cyclohexane (1 minute half-life temperature: 149.2°C), tertiary pentyl peroxide 2-ethylhexyl carbonate (1 minute half-life temperature: 151°C), 1 ,1-Di(tertiary butyl peroxide) cyclohexane (1 minute half-life temperature: 153.8°C), tertiary butyl peroxide isopropyl carbonate (1 minute half-life temperature: 158.8°C), 2, 2-Di(tertiary butyl peroxide) butane (1 minute half-life temperature: 159.9°C), tertiary butyl peroxyacetate (1 minute half-life temperature: 159.9°C), tertiary butyl peroxide- 2-ethylhexyl carbonate (1 minute half-life temperature: 161.4°C), tertiary butyl peroxide-3,3,5-trimethylhexanoate (1 minute half-life temperature: 166°C), tertiary Butyl peroxide benzoate (1 minute half-life temperature: 166.8°C), di-tertiary amyl peroxide (1 minute half-life temperature: 169°C), tertiary butyl cumene peroxide, peroxy Dicumyl oxide, 1,3-bis-(2-tertiarybutylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tertiarybutylperoxy)hexane , Di-tertiary butyl peroxide, and 2,5-dimethyl-2,5-di(tertiary butyl peroxide)-3-hexyne. Each of the initiators can be used alone or in any combination.

In some embodiments of the present invention, the first initiator (C) is selected from the following groups: 1,3-bis-(2-tertiarybutylperoxyisopropyl)benzene, di-tertiary butyl Hydroperoxide, dicumyl benzene hydroperoxide, and 2,5-dimethyl-2,5-bis(tertiary butylperoxy)-3-hexyne.

In some embodiments of the present invention, the second initiator (D) is selected from the following groups: 1,1-di(tertiary butyl peroxide) cyclohexane, tertiary butyl peroxide-2 -Ethylhexyl carbonate, 1,1-di(tertiary hexylperoxy) cyclohexane, and diphenylmethyl peroxide.

In the resin composition of the present invention, based on 100 parts by weight of the resin solid content, the total content of the first starter (C) and the second starter (D) can be 0.01 to 2 parts by weight, for example, 0.02 parts by weight Parts, 0.03 parts by weight, 0.05 parts by weight, 0.07 parts by weight, 0.09 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 0.9 parts by weight, 1 part by weight, 1.2 parts by weight, 1.3 parts by weight, 1.5 parts by weight, or 1.8 parts by weight.

In the resin composition of the present invention, the weight ratio of the first initiator (C) to the second initiator (D) can be 6:1 to 1:6, preferably 6:1 to 3:4, and more Preferably, it is 6:1 to 4:3, such as 5:1, 4:1, 3:1, 5:2, 2:1, 5:3, or 3:2. When the weight ratio of the first starter (C) to the second starter (D) is within the specified range, the prepreg prepared from the resin composition can have better storage stability and shorter required compression time.

1.4. Other optional ingredients as needed

The resin composition of the present invention may further include other optional components as required, such as crosslinking agents, flame retardants, fillers and additives known in the art as exemplified below, to adaptably improve the resin composition in the manufacturing process Processability, or improve the physical and chemical properties of electronic materials made of resin compositions. The additives known in the art include but are not limited to elastomers, co-crosslinking agents and curing accelerators.

[Crosslinking agent]

Herein, the crosslinking agent refers to a component having an unsaturated group that can undergo a crosslinking reaction with polyphenylene ether resin and a component with a maleimide structure to form a three-dimensional network structure. The definition of an unsaturated group is as As mentioned above. In the resin composition of the present invention, the crosslinking agent preferably has good compatibility with the polyphenylene ether resin and the components with the maleimide structure, so that the formed resin composition can have good compatibility after curing. Appearance. Generally speaking, crosslinking agents can be roughly divided into monofunctional crosslinking agents and multifunctional crosslinking agents according to the number of unsaturated groups contained. Among them, the monofunctional crosslinking agent has only one unsaturated group. The multifunctional crosslinking agent has at least two unsaturated groups. In some embodiments of the present invention, in order to make the resin composition have a higher crosslinking density after curing, it is preferable to use a multifunctional crosslinking agent.

Specifically, examples of the crosslinking agent include, but are not limited to, multifunctional allyl compounds, multifunctional acrylates, multifunctional acrylamides, and multifunctional styrenic compounds. Each of the crosslinking agents can be used alone or in any combination.

The polyfunctional allyl compound refers to a compound containing at least two allyl groups. Examples of multifunctional allyl compounds include, but are not limited to, diallyl phthalate, diallyl isophthalate, triallyl isophthalate Tricarboxylate (triallyl trimellitate), triallyl mesate (triallyl mesate), triallyl isocyanurate (TAIC), triallyl cyanurate (triallyl cyanurate, TAC), and prepolymers of the aforementioned compounds.

Multifunctional acrylate refers to a compound containing at least two acrylate groups. Examples of multifunctional acrylates include, but are not limited to, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate (1,6 -hexanediol di(meth)acrylate, ethyleneglycol di(meth)acrylate, propyleneglycol di(meth)acrylate, 1,3-butyl Diol di(meth)acrylate (1,3-butanediol di(meth)acrylate), 1,4-butanediol di(meth)acrylate (1,4-butanediol di(meth)acrylate), ring Cyclohexane dimethanol di(methyl)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate ) Triethylene glycol di(meth)acrylate, and prepolymers containing the aforementioned compounds.

The polyfunctional styrenic compound refers to a compound in which at least two alkenyl groups are attached to the aromatic ring. Examples of multifunctional styrenic compounds include, but are not limited to, 1,3-divinylbenzene, 1,4-divinylbenzene, and trivinylbenzene (1,3-divinylbenzene). trivinylbenzene), 1,3-diisopropenylbenzene (1,3-diisopropenylbenzene), 1,4-diisopropenylbenzene (1,4-diisopropenylbenzene), 1,2-bis(p-vinylphenyl) ethyl Alkane (1,2-bis(p-vinylphenyl)ethane), 1,2-bis(m-vinylphenyl)ethane (1,2-bis(m-vinylphenyl)ethane), 1-(p-vinylphenyl)ethane Yl)-2-(m-vinylphenyl)ethane (1-(p-vinylphenyl)-2-(m-vinylphenyl)-ethane), 1,4-bis(p-vinylphenyl)-ethane ( 1,4-bis(p-vinylphenylethyl)benzene), 1,4-bis(m-vinylphenylethyl)benzene (1,4-bis(m-vinylphenylethyl)benzene), 1,3-bis(p-vinylphenylethyl)benzene 1,3-bis(p-vinylphenylethyl)benzene (1,3-bis(p-vinylphenylethyl)benzene), 1,3-bis(m-vinylphenylethyl)benzene (1,3-bis(m-vinylphenylethyl)benzene), 1-(p-vinylphenylethyl)-4-(m-vinylphenylethyl) benzene), 1-(p-vinylphenylethyl) benzene 1-(p-vinylphenylethyl)-3-(m-vinylphenylethyl)benzene), and prepolymers containing the foregoing compounds.

Considering the compatibility between the components of the resin composition of the present invention, the crosslinking agent is preferably selected from the following groups: TAIC, TAC, 1,3-divinylbenzene, 1,4-divinylbenzene, 1, 2-bis(p-vinylphenyl)ethane, 1,2-bis(m-vinylphenyl)ethane, 1-(p-vinylphenyl)-2-(m-vinylphenyl)ethane, And the aforementioned combination. In the following examples, TAIC is used as the crosslinking agent.

In the resin composition of the present invention, based on 100 parts by weight of the solid resin content, the content of the crosslinking agent may be 0 parts by weight to 40 parts by weight, more specifically, 5 parts by weight to 35 parts by weight, for example, 7 parts by weight , 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight, 30 parts by weight, or 32 parts by weight.

[Flame retardant]

If necessary, the resin composition may further contain a flame retardant to increase the heat resistance and flame retardancy of the prepared electronic material. The types of flame retardants include, but are not limited to, phosphorus-containing flame retardants, bromine-containing flame retardants, and nitrogen-containing compounds, and each type of flame retardant can be used alone or in any combination.

Examples of phosphorus-containing flame retardants include, but are not limited to, phosphate ester, phosphazene, ammonium polyphosphate, metal phosphinate, and melamine phosphate (melamine phosphate) . Each phosphorus-containing flame retardant can be used alone or in any combination. Examples of hypophosphorous acid metal salts include, but are not limited to, dialkyl aluminum hypophosphite, tris(diethyl hypophosphite) aluminum, tris(methyl ethyl hypophosphite) aluminum, tris(diphenyl hypophosphite) aluminum, double (Diethyl hypophosphorous acid) zinc, bis (methyl ethyl hypophosphorous acid) zinc, bis (diphenyl hypophosphorous acid) zinc, bis (diethyl hypophosphorous acid) titanium oxide, bis (methyl ethyl hypophosphorous acid) Titanium oxide, and bis(diphenyl hypophosphorous acid) titanium oxide. Commercially available metal hypophosphites include the OP935 product available from CLARIANT.

Examples of bromine-containing flame retardants include, but are not limited to, tetrabromobisphenol A, decabromodiphenyl oxide, decabrominated diphenyl ethane, 1, 2 -Di(tribromophenyl)ethane (1,2-bis(tribromophenyl) ethane), brominated epoxy oligomer, octabromotrimethylphenyl indane, bis( 2,3-dibromopropyl ether) (bis(2,3-dibromopropyl ether)), tris(tribromophenyl) triazine (tris(tribromophenyl) triazine), brominated aliphatic hydrocarbon (brominated aliphatic hydrocarbon), and bromine Brominated aromatic hydrocarbon (brominated aromatic hydrocarbon). Examples of nitrogen-containing compounds include, but are not limited to, melamine and its derivatives.

In the resin composition of the present invention, based on 100 parts by weight of the resin solid content, the content of the flame retardant may be 0 parts by weight to 30 parts by weight, more specifically 5 parts by weight to 25 parts by weight, for example, 7 parts by weight , 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, or 23 parts by weight. However, the present invention is not limited to this, and those skilled in the art to which the present invention pertains can make adjustments according to actual needs.

[filler]

The resin composition may further include fillers to improve the mechanical strength, thermal conductivity, and dimensional stability of the prepared electronic material. Examples of suitable fillers include, but are not limited to, fillers selected from the following groups: silica, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, aluminum oxide, aluminum hydroxide, boron nitride, Silicon nitride, aluminum silicon carbide, silicon carbide, sodium carbonate, magnesium carbonate, titanium dioxide, zinc oxide, zirconia, quartz, diamond powder, diamond-like powder, graphite, calcined kaolin, kaolin, mica, hydrotalcite, PTFE powder , Glass beads, ceramic whiskers, carbon nanotubes, nano-grade inorganic powders, and combinations of the foregoing.

Generally speaking, based on 100 parts by weight of the total solid content of the resin composition, the content of the filler may be 0 parts by weight to 40 parts by weight, for example, 5 parts by weight, 7 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight. Parts, 18 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, or 35 parts by weight, but the present invention is not limited thereto, and those skilled in the art to which the present invention belongs can adjust according to actual needs.

1.5. Preparation of resin composition

Regarding the preparation of the resin composition of the present invention, each component of the resin composition, including polyphenylene ether resin with unsaturated group at the end, component with maleimide structure, first initiator, second The starting agent and other optional ingredients are uniformly mixed with a stirrer and dissolved or dispersed in a solvent to form a varnish-like form for subsequent processing and utilization. The solvent can be any inert solvent that can dissolve or disperse the components of the resin composition, but does not react with the components. For example, the solvent that can be used to dissolve or disperse each component of the resin composition includes but is not limited to: toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, methyl isobutyl ketone, N,N-dimethyl formamide (N,N-dimethyl formamide, DMF), N,N-dimethyl acetamide (DMAc), and N-methyl pyrrolidone (N -methyl-pyrolidone, NMP). Each solvent can be used alone or in combination. The amount of the solvent is not particularly limited, as long as it can uniformly dissolve or disperse the components of the resin composition in principle. In the following examples, methyl ethyl ketone is used as the solvent.

2. Prepreg

The present invention also provides a prepreg prepared from the above resin composition, which is prepared by impregnating or coating a substrate with the above resin composition and drying the impregnated or coated substrate. Methods of impregnating or coating the resin composition include, but are not limited to, dipping, roll coating, die coating, bar coating, gravure coating, spin coating, slit coating, and spraying. The impregnated or coated substrate can be dried at a temperature of 80°C to 180°C for 1 to 20 minutes to obtain a prepreg in a semi-cured state (B-stage). In the attached examples, the drying is performed at 175°C for 2 to 15 minutes.

Commonly used substrates include but are not limited to paper, cloth or felt made from materials selected from the following groups: paper fiber, glass fiber, quartz fiber, organic polymer fiber, carbon fiber, and combinations of the foregoing. Examples of organic polymer fibers include, but are not limited to, high-modulus polypropylene (HMPP) fibers, polyamide fibers, ultra-high molecular weight polyethylene (UHMWPE) fibers, and liquid crystal polymerization物 (liquid crystal polymer, LCP). In some embodiments of the present invention, glass fiber cloth is used as the substrate, such as E-glass fiber cloth, NE-grade glass fiber cloth, Q-grade glass fiber cloth, and D-grade glass fiber cloth. , S grade glass fiber cloth, and L grade glass fiber cloth, and the glass fiber cloth can be woven or non-woven. In the attached examples, E-grade glass fiber cloth is used as the substrate.

3. Metal foil laminated board and printed circuit board

The present invention also provides a metal foil laminated board made from the above-mentioned prepreg, which comprises a composite layer and a metal layer, wherein the composite layer is provided by the aforementioned prepreg. Specifically, the metal foil laminated board of the present invention can be prepared by laminating a plurality of layers of prepregs, and then laminating a metal foil (such as copper foil) on at least one outer surface of the composite layer formed by the laminated prepregs to provide A laminate comprising a composite layer and a metal layer is subjected to a hot pressing operation to obtain a metal foil laminate. The conditions of the hot pressing operation can be as follows: at a temperature of 180°C to 220°C and a pressure of 5 kg/cm 2 (kg/cm ² ) to 15 kg/cm 2, heating for 60 to 200 minutes Pressure.

The metal foil laminated board can be further patterned with the metal foil on the outer side to form a printed circuit board.

4. Example

4.1. Measurement method description

The following specific implementations are used to further illustrate the present invention, in which the measuring instruments and methods used are as follows:

[Glass transition temperature (Tg) test]

Use a dynamic mechanical analyzer (differential scanning calorimeter, DSC) to measure the glass transition temperature (Tg) of the metal foil laminate. The Tg test specification is the IPC-TM-650.2.4.24C and 25C test methods of the Institute for Interconnecting and Packaging Electronic Circuits (IPC). The metal foil laminated board made from the resin composition of the present invention can judge the degree of curing through the measured Tg. Specifically, in a resin composition system mainly composed of polyphenylene ether resin and maleimide-based components, when Tg reaches 220°C, it means that the metal foil laminate has reached a fully cured state (ie C-stage ( C-stage)). In other words, if the Tg of the metal foil laminated board produced by the 120-minute hot pressing operation still fails to reach 220°C, it means that the fully cured state has not been reached, and a longer pressing time is required.

[Dip solder resistance test]

Soak the dried metal foil laminate in a soldering bath at 288°C for 20 seconds and then take it out. Repeat the above immersion and take-out action, and observe whether the plate bursts, for example, observe whether the metal foil laminate has delamination or swelling Bubble situation. Record the number of soaking times for the metal foil laminate to burst.

[Dielectric constant (Dk) and dielectric loss factor (Df) test]

According to the IPC-TM-650 2.5.5.13 specification, the dielectric constant (Dk) and dielectric loss factor (Df) of the dielectric layer (resin content (RC) is 70%) are measured at a working frequency of 10 GHz ), the dielectric layer refers to the product obtained by etching and removing the double-sided metal foil of the metal foil laminate.

[Dynamic viscosity test]

Knead the newly prepared prepreg and the prepreg after 1 week to 11 weeks to produce powder, take 0.45 g of powder and place it in a rheometer (model: HR-1, manufactured by TA Instrument). Measurement of dynamic viscosity. The measurement interval of the prepreg after 1 week to 11 weeks is one week, that is, the measurement interval is as follows: after 1 week, 2 weeks,..., 10 weeks, 11 weeks. The measurement conditions are as follows: the heating rate is 2.5°C/min, the measurement temperature range is 50°C to 180°C, and the lowest viscosity value is taken and recorded. The unit of dynamic viscosity is "Pa·s".

4.2. List of raw material information used in Examples and Comparative Examples

Table 1: List of raw material information Raw material model Description SA 9000 Polyphenylene ether resin with unsaturated groups at the end, purchased from Saudi Basic Industries BMI-70 Ingredients with maleimide structure (BMI ingredients), purchased from KI Chemical TAIC Crosslinking agent, triallyl isocyanurate, purchased from Evonik Perbutyl P Initiator, 1,3-bis-(2-tertiarybutylperoxyisopropyl)benzene, with a 1-minute half-life temperature of 175.4°C, purchased from NOF Corporation Perbutyl D Starter, di-tertiary butyl peroxide, 1 minute half-life temperature of 185.9°C, purchased from Japan Oil Peroxan IHP-50 Initiator, dicumyl benzene hydroperoxide, 1 minute half-life temperature of 207°C, purchased from PERGAN Perhexyne 25B Initiator, 2,5-dimethyl-2,5-di(tertiary butylperoxy)-3-hexyne, 1 minute half-life temperature of 194.3°C, purchased from Japan Oil Perhexa C-79(S) Starter, 1,1-bis(tertiary butylperoxy) cyclohexane, with a 1-minute half-life temperature of 153.8°C, purchased from Japan Oil Perbutyl E Starter, tertiary butylperoxy-2-ethylhexyl carbonate, 1 minute half-life temperature of 161.4°C, purchased from Japan Oil Perhexa HC Starter, 1,1-bis(tertiary hexyl peroxide) cyclohexane, 1 minute half-life temperature of 149.2°C, purchased from Japan Oil Nyper BW Initiator, dibenzoyl peroxide, 1 minute half-life temperature of 130°C, purchased from Japan Oil Peroxan CU-90 L Initiator, cumene hydroperoxide, 1 minute half-life temperature of 222°C, purchased from Bojin 525ARI SiO ₂ filler, purchased from Sibelco OP-935 Flame retardant, diethyl aluminum hypophosphite, purchased from Clariant MEK Solvent, methyl ethyl ketone, purchased from TRANS CHIEF CHEMICAL

4.3. Preparation of resin composition

The resin compositions of Examples 1 to 6 and Comparative Examples 1 to 8 were prepared in the proportions shown in Table 2-1 to Table 2-3, in which the components were mixed at room temperature using a stirrer, and MEK was added as a solvent Then, after the resulting mixture is stirred at room temperature for 60 to 120 minutes, each resin composition is prepared.

Table 2-1: Composition of the resin composition of the example Unit: parts by weight Example 1 2 3 4 5 6 Polyphenylene ether resin (A) SA 9000 100 100 100 100 100 100 BMI ingredients (B) BMI-70 100 100 100 100 100 100 Crosslinking agent TAIC 70 70 70 70 70 70 The first initiator (C) Perbutyl P 0.6 0.4 Perbutyl D 0.5 0.3 0.3 Peroxan IHP-50 0.4 The second initiator (D) Perhexa C-79(S) 0.1 0.3 0.2 0.4 Perbutyl E 0.3 Perhexa HC 0.4 Flame retardant OP-935 30 30 30 30 30 30 filler 525ARI 90 90 90 90 90 90 Solvent MEK 200 200 200 200 200 200 The first initiator (C): the second initiator (D) (weight ratio) 6:1 4:3 5:2 4:3 3:4 3:4 The difference between the first 1-minute half-life temperature and the second 1-minute half-life temperature (°C) 21.6 21.6 32.1 45.6 32.1 36.7

Table 2-2: Composition of the resin composition of Comparative Examples 1 to 4 Unit: parts by weight Comparative example 1 2 3 4 Polyphenylene ether resin (A) SA 9000 100 100 100 100 BMI ingredients (B) BMI-70 100 100 100 100 Crosslinking agent TAIC 70 70 70 70 The first initiator (C) Perbutyl P 0.7 Perbutyl D 0.6 0.4 The second initiator (D) Perhexa C-79(S) 0.7 Nyper BW 0.1 0.3 Flame retardant OP-935 30 30 30 30 filler 525ARI 90 90 90 90 Solvent MEK 200 200 200 200 The first initiator (C): the second initiator (D) (weight ratio) 7:0 0: 7 6:1 4:3 The difference between the first 1-minute half-life temperature and the second 1-minute half-life temperature (°C) 55.9 55.9

Table 2-3: Composition of the resin composition of Comparative Examples 5 to 8 Unit: parts by weight Comparative example 5 6 7 8 Polyphenylene ether resin (A) SA 9000 100 100 100 100 BMI ingredients (B) BMI-70 100 100 100 100 Crosslinking agent TAIC 70 70 70 70 The first initiator (C) Peroxan CU-90L 0.4 Perbutly P 0.5 Perhexyne 25B 0.2 Perbutyl E 0.6 The second initiator (D) Perbutyl D 0.3 Nyper BW 0.1 Perbutyl E 0.2 Perbutly P 0.5 Flame retardant OP-935 30 30 30 30 filler 525ARI 90 90 90 90 Solvent MEK 200 200 200 200 The first initiator (C): the second initiator (D) (weight ratio) 4:3 6:1 5:2 2:5 The difference between the first 1-minute half-life temperature and the second 1-minute half-life temperature (°C) 36.1 31.4 14 18.9

4.4. Preparation and quality testing of prepreg and metal foil laminate

The resin compositions of Examples 1 to 6 and Comparative Examples 1 to 8 were used to prepare prepregs and metal foil laminates. First, through a roll coater, immerse glass fiber cloth (model: 2116, thickness: 0.09 mm) into the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 8, and control the thickness of the glass fiber cloth To the appropriate level. Then, the impregnated glass fiber is placed in a dryer at 175°C and heated and dried for 2 to 15 minutes to obtain a semi-cured state (B-stage) prepreg (the resin content of the prepreg is 70%). After that, the four prepregs were laminated, and a 0.5 ounce copper foil was laminated on each of the outermost layers on both sides, and then placed in a hot press for high-temperature hot-press curing. The hot pressing conditions are: heating up to 200°C at a heating rate of 3.0°C/min, and hot pressing at a pressure of 15 kg/cm² (initial pressure 8 kg/cm²) at 200°C for 120 minutes . In this way, a metal foil laminated board is produced.

Measure the properties of the prepregs and metal foil laminates of Examples 1 to 6 and Comparative Examples 1 to 8 according to the measurement methods described above, including dynamic viscosity, Tg, solder dip resistance, Dk and Df, and record the results in In Table 3-1, Table 3-2, Table 4-1 and Table 4-2.

Table 3-1: Dynamic viscosity of the prepregs of the examples Unit: Pa·s Example 1 2 3 4 5 6 When preparation is complete 339 351 341 360 354 351 After 1 week 339 351 341 363 354 355 After 2 weeks 342 352 343 368 355 358 After 3 weeks 342 352 342 372 355 361 After 4 weeks 344 356 345 377 359 366 After 5 weeks 339 360 341 380 363 371 After 6 weeks 338 364 342 387 367 375 After 7 weeks 348 366 350 395 369 383 After 8 weeks 341 369 348 399 372 389 After 9 weeks 340 374 346 410 377 395 After 10 weeks 340 377 350 417 380 400 After 11 weeks 342 382 351 421 385 409

Table 3-2: Properties of the prepregs and metal foil laminates of the examples Tg Dip solder resistance Dk @ 10GHz Df@ 10GHz unit °C frequency Example 1 220 ＞20 3.5 0.0045 2 221 ＞20 3.5 0.0045 3 220 ＞20 3.5 0.0045 4 220 ＞20 3.5 0.0045 5 220 ＞20 3.5 0.0045 6 220 ＞20 3.5 0.0045

Table 4-1: Dynamic viscosity of the prepreg of the comparative example Unit: Pa·s Comparative example 1 2 3 4 5 6 7 8 When preparation is complete 350 345 349 330 336 340 345 319 After 1 week 348 347 355 347 336 346 345 317 After 2 weeks 351 345 361 350 336 349 348 317 After 3 weeks 352 349 368 355 337 351 348 318 After 4 weeks 356 362 374 362 336 367 350 320 After 5 weeks 349 383 381 383 337 385 345 321 After 6 weeks 355 389 389 389 338 391 344 321 After 7 weeks 359 402 400 412 338 410 354 321 After 8 weeks 349 422 417 441 343 426 347 322 After 9 weeks 348 435 423 460 340 440 346 321 After 10 weeks 353 471 433 491 339 480 346 323 After 11 weeks 359 497 467 560 340 502 350 323

Table 4-2: Properties of the prepreg and metal foil laminate of the comparative example Tg Dip solder resistance Dk @ 10GHz Df@ 10GHz unit °C frequency Comparative example 1 217 ＞20 3.5 0.0045 2 221 ＞20 3.5 0.0045 3 220 ＞20 3.5 0.0045 4 221 ＞20 3.5 0.0045 5 206 ＞20 3.5 0.0045 6 220 ＞20 3.5 0.0045 7 218 ＞20 3.5 0.0045 8 216 ＞20 3.5 0.0045

As shown in Table 3-1 and Table 3-2, the electronic materials prepared by using the resin composition of the present invention can achieve satisfactory performance in all physical and chemical properties and dielectric properties (such as Dk, Df, solder resistance, etc.) The degree of satisfaction. In particular, the prepreg prepared by using the resin composition of the present invention can have both good storage stability (that is, a lower long-term dynamic viscosity change rate) and a shorter required pressing time (the Tg is uniform after 120 minutes of pressing) Above 220°C, it shows that it has reached the fully cured state, namely C-stage). In addition, the comparison of Examples 1, 2, 3, and 5 with Examples 4 and 6 shows that when the first 1-minute half-life temperature is higher than the second 1-minute half-life temperature by 20°C to 35°C, the prepared prepreg The long-term dynamic viscosity change rate can be further reduced, that is, storage stability can be further improved.

In contrast, as shown in Table 4-1 and Table 4-2, the prepreg made with the resin composition of the present invention cannot have both good storage stability and a short pressing time. That is, a proper balance cannot be achieved between storage stability and pressing time, and the effects of the present invention cannot be provided. Specifically, Comparative Examples 1 and 2 show that when the resin composition contains only one initiator, the prepared prepreg cannot have both good storage stability and a short pressing time. Comparative Examples 3, 4, 7 and 8 show that when the resin composition contains two kinds of starters, if the difference between the first 1-minute half-life temperature and the second 1-minute half-life temperature exceeds the specified range of the present invention, even The first 1-minute half-life temperature is within the specified range, and the prepared prepreg still cannot have good storage stability and a short pressing time. In addition, Comparative Examples 5 and 6 show that when the resin composition contains two initiators, if the first 1-minute half-life temperature is higher or lower than the specified range of the present invention, even if the first 1-minute half-life temperature is The temperature difference of the second one-minute half-life is within the specified range, and the prepared prepreg still cannot have both good storage stability and short pressing time. The above experimental results fully show that the resin composition of the present invention can indeed provide unexpected effects through a combination of specific components, including an initiator with a specific half-life temperature condition.

The above-mentioned embodiments are merely illustrative to illustrate the principles and effects of the present invention, and to illustrate the technical features of the present invention, not to limit the protection scope of the present invention. Any changes or arrangements that can be easily made by those skilled in the art without departing from the technical principles and spirit of the present invention fall within the claimed scope of the present invention. Therefore, the protection scope of the present invention is as listed in the attached patent scope.

no

no

Claims (13)

A resin composition comprising: (A) Polyphenylene ether resin with unsaturated groups at the end; (B) Ingredients with maleimide structure; (C) a first initiator, the first initiator having a first 1-minute half-life temperature; and (D) The second initiator, which has a second 1-minute half-life temperature, The first 1-minute half-life temperature is higher than the second 1-minute half-life temperature by 20°C to 50°C, and the first 1-minute half-life temperature is 170°C to 220°C. The resin composition of claim 1, wherein the first one-minute half-life temperature is 21°C to 35°C higher than the second one-minute half-life temperature. The resin composition of claim 1, wherein the weight ratio of the first initiator (C) to the second initiator (D) is 6:1 to 1:6. The resin composition of claim 1, wherein the polyphenylene ether resin (A) having an unsaturated group at the end is represented by the following formula (I):

Formula (I), in formula (I), R ₃ , R ₄ , R ₅ , and R ₆ are each independently H, or a C1 to C5 alkyl group that is or unsubstituted; m and n are each independently 0 An integer to 100, provided that m and n are not at the same time as 0; Z is not present, -O-,

,

,

,

,

, Or aryl, wherein R ₇ and R ₈ are each independently H or C1 to C12 alkyl; X and Y are each independently non-existent, carbonyl group, or group with alkenyl; And A ₁ and A ₂ are independently

,,

,

,

or

. The resin composition of claim 1, wherein the component (B) having a maleimide structure is selected from the following group: 1,2-bismaleimide ethane, 1,6-bismaleimide Leximinohexane, 1,3-bismaleimidobenzene, 1,4-bismaleimidobenzene, 2,4-bismaleimidotoluene, 4,4 '-Bismaleimidodiphenylmethane, 4,4'-bismaleimidodiphenyl ether, 3,3'-bismaleimidodiphenylmethane, 4, 4'-bismaleimidodiphenyl sulfide, 4,4'-bismaleimidodicyclohexylmethane, 3,5-bis(4-maleimidphenyl)pyridine , 2,6-bismaleiminopyridine, 1,3-bis(maleiminomethyl)cyclohexane, 1,3-bis(maleiminomethyl)benzene, 1,1-bis(4-maleimidphenyl)cyclohexane, 1,3-bis(dichloromaleimidyl)benzene, 4,4'-dicitraconyl Diphenylmethane (4,4'-biscitraconimidodiphenylmethane), 2,2-bis(4-maleiminophenyl) propane, 1-phenyl-1,1-bis(4-maleimide) Phenyl)ethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-dibenzyl bismaleimide, α,α-bis(4-male Leximinophenyl) toluene, 3,5-bismaleimino-1,2,4-triazole, N,N'-ethylenebismaleimide, N,N' -Hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N' -4,4'-Diphenylmethane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N'-4,4'-diphenyl Base bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-α,α'-4,4'-dimethylene ring Hexane bismaleimide, N,N'-m-xylene bismaleimide, N,N'-4,4'-diphenylcyclohexane bismaleimide, N,N '-Methylene bis(3-chloro-p-phenylene) bismaleimide, and combinations of the foregoing. For the resin composition of claim 1, the first initiator (C) is selected from the following group: 4,4-bis(tertiary butylperoxy) n-butyl valerate (n-butyl 4,4- bis(tert-butylperoxy)valerate), tert-butylcumyl peroxide (tert-butylcumyl peroxide), dicumyl peroxide (dicumyl peroxide), 1,3-bis-(2-tert-butylperoxy) Isopropyl peroxide) benzene (1,3-di-(2-tert-butyl-peroxyisopropyl)benzene), 2,5-dimethyl-2,5-di-(tert-butyl-peroxyisopropyl) hexane (2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane), di-tert-butylperoxide, 2,5-dimethyl-2,5- Di(tert-butylperoxy)-3-hexyne (2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne), diisopropylbenzene hydroperoxide, P-menthane hydroperoxide, and combinations of the foregoing. For the resin composition of claim 1, the second initiator (D) is selected from the following group: 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy) hexamethylene Alkane (2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1,1,3 ,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate (tert-amylperoxy-2-ethylhexanoate), dibenzoyl peroxide, tertiary hexyl peroxide -2-ethylhexanoate (tert-hexylperoxy-2-ethylhexanoate), tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate Ester (tert-butylperoxyisobutyrate), 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane (1,1-di(tert-butylperoxy)-3,3, 5-trimethylcyclohexane), 1,1-di(tert-hexylperoxy)cyclohexane (1,1-di(tert-hexylperoxy)cyclohexane), tert-pentyl 2-ethylhexyl carbonate (tert- amylperoxy-2-ethyl hexylcarbonate), 1,1-di(tert-butylperoxy)cyclohexane (1,1-di(tert-butylperoxy)cyclohexane), tert-butylperoxy isopropyl carbonate ( tert-butylperoxyisopropylcarbonate, 2,2-di(tert-butylperoxy)butane (2,2-di(tert-butylperoxy)butane), tert-butylperoxyacetate, tertiary Tert-butylperoxy-2-ethylhexylcarbonate (tert-butylperoxy-2-ethylhexylcarbonate), tert-butylperoxy-3,3,5-trimethylhexanoate (tert-butylperoxy-3,3, 5-trimethylhexanoate), tert-butylperoxybenzoate (tert-butylperoxybenzoate), di-tert-amylperoxide (di-tert-amylperoxide), tert-butyl cumene peroxide, peroxide Diisopropylbenzene, 1,3 -Bis-(2-tertiary butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tertiary butylperoxy)hexane, di-tertiary butylperoxy , 2,5-Dimethyl-2,5-di(tertiarybutylperoxy)-3-hexyne, and combinations of the foregoing. The resin composition according to any one of claims 1 to 7, further comprising a crosslinking agent selected from the following group: polyfunctional allylic compound, polyfunctional acrylate acrylate, polyfunctional acrylamide, polyfunctional styrenic compound, and combinations of the foregoing. The resin composition according to any one of claims 1 to 7, further comprising a flame retardant selected from the group consisting of phosphorus-containing flame retardants, bromine-containing flame retardants, nitrogen-containing compounds, and combinations of the foregoing. The resin composition according to any one of claims 1 to 7, further comprising a filler selected from the following group: silica, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, oxide Aluminum, aluminum hydroxide, boron nitride, silicon nitride, aluminum silicon carbide, silicon carbide, sodium carbonate, magnesium carbonate, titanium dioxide, zinc oxide, zirconia, quartz, diamond powder, diamond-like powder, graphite, calcined kaolin, Bailing Soil, mica, hydrotalcite, polytetrafluoroethylene (PTFE) powder, glass beads, ceramic whiskers, carbon nanotubes, nano-grade inorganic powder, and combinations of the foregoing. A prepreg, which is prepared by impregnating or coating a substrate with the resin composition according to any one of claims 1 to 10, and drying the impregnated or coated substrate. A metal foil laminated board, which is produced by laminating the prepreg as described in claim 11 and metal foil. A printed circuit board, which is made of the laminated board as described in claim 12.